EP2818155A1 - Hair conditioner - Google Patents

Hair conditioner Download PDF

Info

Publication number
EP2818155A1
EP2818155A1 EP20130382248 EP13382248A EP2818155A1 EP 2818155 A1 EP2818155 A1 EP 2818155A1 EP 20130382248 EP20130382248 EP 20130382248 EP 13382248 A EP13382248 A EP 13382248A EP 2818155 A1 EP2818155 A1 EP 2818155A1
Authority
EP
European Patent Office
Prior art keywords
composition
acid
composition according
carbon atoms
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20130382248
Other languages
German (de)
French (fr)
Inventor
Pilar CASTÁN BARBERÁN
Judit RODRÍGUEZ COSTERO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp SA
Original Assignee
Kao Corp SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corp SA filed Critical Kao Corp SA
Priority to EP20130382248 priority Critical patent/EP2818155A1/en
Priority to PCT/EP2014/063119 priority patent/WO2014206920A1/en
Priority to MX2015016500A priority patent/MX353750B/en
Priority to PT147340749T priority patent/PT3013312T/en
Priority to BR112015032424-0A priority patent/BR112015032424B1/en
Priority to DK14734074.9T priority patent/DK3013312T3/en
Priority to EP14734074.9A priority patent/EP3013312B1/en
Priority to JP2016522425A priority patent/JP6194420B2/en
Priority to RU2016102165A priority patent/RU2676695C2/en
Priority to CA2914141A priority patent/CA2914141C/en
Priority to US14/901,369 priority patent/US10617619B2/en
Priority to ES14734074.9T priority patent/ES2648598T3/en
Priority to PL14734074T priority patent/PL3013312T3/en
Publication of EP2818155A1 publication Critical patent/EP2818155A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/416Quaternary ammonium compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216Solid or semisolid forms
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/342Alcohols having more than seven atoms in an unbroken chain
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365Hydroxycarboxylic acids; Ketocarboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42Amides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/12Preparations containing hair conditioners
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59Mixtures
    • A61K2800/592Mixtures of compounds complementing their respective functions

Definitions

  • the present invention relates to a composition (hereafter also referred to as a cosmetic composition) comprising one or more quaternary ester ammonium compounds, one or more amidoamine compounds and one or more fatty alcohols. Also, the present invention relates to cosmetic compositions being solid at room temperature, and to a liquid hair conditioner composition that can be prepared from that solid cosmetic compositions, and a method to prepare a liquid hair conditioner composition by dispersing said solid cosmetic composition in water at moderate temperatures.
  • Human hair can become soiled from the contact with environment and from sebum secreted by the scalp. This soiling may cause the hair to have a dirty or greasy feel, and an unattractive appearance.
  • Shampooing cleans the hair by removing the excess of soil and sebum.
  • shampooing can leave the hair in a wet, tangled and generally unmanageable state. Once the hair dries, it is often left in a dry, rough, lusterless or frizzy condition due to the removal of the hair's natural oils and other natural conditioning and moisturizing components. It can be also left with increased levels of static upon drying which can interfere with combing, brushing and styling of hair.
  • Hair conditioning compositions are widely known and are typically applied to the hair immediately after shampooing and rinsing the hair to avoid the problems described above and provides conditioning effect to the hair. The conditioning composition is worked through the hair, and may be then used as a leave-on conditioner or it can be rinsed from the hair with water.
  • hair conditioning compositions have used cationic surfactants.
  • Cationic surfactants are those in which the surfactant activity resides in the positively charged cation portion of the molecule. The cationic surfactants are therefore attracted to the negatively charged hair surface and deposited on the hair.
  • cationic surfactants quaternary ammonium compounds and alkyl amidoamine compounds are particularly suited to the treatment of human hair.
  • many hair conditioning products are based on quaternary ammonium compounds and alkyl amidoamine compounds.
  • hair conditioner compositions found in the market are liquid preparations while some of the cationic surfactants used as ingredients of said preparations are solid at room temperature and not dispersible in water at room temperature; even when previously melted, in order the cationics are dispersed in water it is need water temperature at least of 50-60°C.
  • In order to disperse them in water it is needed or using water a temperature around 80°C or melt the amidoamine an disperse it in water heated at around 60°C.
  • the need of a melting step together with the need of using hot water involves energy consumption.
  • a way to eliminate the need of a melting step and simplify the hair conditioner preparation process is having a solid cosmetic composition which comprises one or more quaternary compounds as ingredient while being easily dispersible in water at moderate temperatures or even room temperature.
  • EP0786250 describes an aqueous formulation for conditioning hair comprising an active substance mixture comprising quaternary ammonium compounds (0.01-30%wt) and alkyl amidoamine compounds (0.01-30% wt) in addition to standard components.
  • the treatment of human hair with the disclosed compositions lead to a good wet and dry combing advantageous coupled with good hair maintenance and low tendency to static electricity.
  • US20040146478 describes the use of mixtures comprising quaternary ammonium compounds and fatty acid amidoamine compounds for cosmetic preparations, especially for hair conditioner preparations, preferably in an emulsion form.
  • the problem addressed was to provide transparent cosmetic preparations, more especially for hair care and particularly for conditioning the hair, which would allow the storage- and temperature-stable incorporation both of silicone oils and of antidandruff agent.
  • EP2394632 describes a hair conditioner composition being a solid or paste form at ambient temperature, aimed to provide an easily-handled hair conditioning composition with a very low water content and a low energy method of producing the same.
  • the composition disclosed comprises a component (a) including higher alcohol with 16 carbon atoms or more, higher fatty acid with 16 carbon atoms or more and/or their derivatives, a component (b) being a cationic surfactant and a component (c) including polyhydric alcohol and/or polyethylene glycol having a melting point of 70°C or less.
  • compositions that provide very good performance, particularly in terms of combing force and/or antistatic effect, especially advantageous for damaged hair, wherein the composition comprises quaternary ester ammonium compounds and alkyl amidoamine compounds in certain ratios, together in combination with fatty alcohols.
  • Another object of the present invention is to provide a composition that is solid at room temperature.
  • Another object of the present invention is to provide a hair conditioner composition and a method to prepare a hair conditioner composition by dispersing the solid composition according to the invention in water at moderate temperatures, thus obtaining a liquid hair conditioner.
  • the present invention provides a composition, said composition comprising:
  • the composition is generally a cosmetic composition or a composition used for the manufacture of a cosmetic composition.
  • the present invention provides a room temperature solid cosmetic composition, said composition comprising:
  • the present invention provides a hair conditioner composition comprising:
  • the present invention provides a method to prepare a hair conditioner composition by dispersing the solid cosmetic composition according to the second aspect of the present invention in water at a temperature within a range of 15°C to 40°C, preferably within a range of 18 to 35°C, more preferably within a range of 20 to 30°C, most preferably at room temperature.
  • the present invention provides a use of the hair conditioner composition according to the third aspect of the present invention or obtained according to the fourth aspect of the present invention for the conditioning treatment of hair.
  • room temperature is understood as a temperature in the range of 20°C to 25°C.
  • Active weight is the weight of the active matter with respect to the total weight of the composition, wherein by active matter it is understood the set of specific components responsible for a certain action.
  • the active matter is the totality of ingredients, from which are derived all or part of its effectiveness, particularly components (a), (b), and (c).
  • the main object of the present invention is a composition comprising:
  • the one or more amidoamine compounds (b) is behenamidopropyl dimethylamine.
  • the present invention comprises one or more quaternary ester ammonium compounds (a), commonly known as esterquat, wherein the one or more quaternary ester ammonium compounds (a) preferably comprise at least a compound of formula (I) or even more preferably the one or more quaternary ester ammonium compounds (a) are all represented by formula (I) : wherein X 1 represents an hydroxyalkyl group containing 1 to 4 carbon atoms or an alkyl group containing 1 to 4 carbon atoms or an alkyl group containing one aromatic group, preferably X 1 is an alkyl group containing 1 to 4 carbon atoms, more preferably X 1 is a methyl group; R 1 is a linear or branched alkyl or alkenyl group containing from 5 to 23 carbon atoms and from 0 to 3 double bonds, R 2 and R 3 each independently represent H, OH or -O-L q -C(O)-R 1 , L represents a -(OCH 2
  • the quaternary ammonium compound of the invention are preferably non-ethoxylated, non-propoxylated.
  • n, and p are equal to 2. In another preferred embodiment m and p are equal to 2 and n is equal to 1.
  • q represents an average number within the range of 0 to 10, more preferably within the range of 0 to 6, most preferred 0.
  • A preferably represents an halide, phosphate or alkylsulphate, more preferably an alkylsulphate, most preferred methylsulphate.
  • the quaternary ester ammonium compound of the invention is an ethoxylated and/or propoxylated esterquat.
  • the order of sequence of the ethylene oxide and propylene oxide groups is not critical for the invention.
  • the one or more quaternary ester ammonium compounds (a) of formula (I) comprises a mixture of at least one or more mono-quaternary ester ammonium compounds, di-quaternary ester ammonium compounds or tri-quaternary ester ammonium compounds of formula (I.1), (I.2) and (I.3).
  • R 2 and R 3 each independently represent -H, or -OH
  • X 1 represents an hydroxyalkyl group containing 1 to 4 carbon atoms or an alkyl group containing 1 to 4 carbon atoms or an alkyl group containing one aromatic group, preferably X 1 is an alkyl group containing 1 to 4 carbon atoms, more preferably X 1 is a methyl group
  • R 1 is a linear or branched alkyl or alkenyl group containing from 5 to 23 carbon atoms and from 0 to 3 double bonds
  • L represents a -(OCH 2 CH 2 )a-(OR 4 CHCH 2 ) b - group, wherein R 4 represents an alkyl group containing 1-4 carbon atoms, a represents an average number within the range of 0 to 20, b represents an average number within the range of 0 to 6, and the sum of a+b represents an average number within the range of 0 to 26, preferably from 0 to 10, more
  • the one or more quaternary ester ammonium compounds (a) are obtained from triethanolamine or methyldiethanolamine or mixtures thereof, preferably from triethanolamine.
  • the compound of formula (I) is prepared by reacting triethanolamine or methyldiethanoalime or mixtures thereof, preferably triethanolamine, with a compound of formula R 1 COOH or a derivative thereof (e.g. a chloride, anhydride or ester thereof) wherein R' is as hereinbefore defined.
  • the compound of formula R 1 COOH is a C8-24 fatty acid.
  • the fatty acid may be a natural product obtained from the oils and fats of plants and animals, such as palm, sunflower, soybean, olive, canola, tallow and tall oil. Alternatively a synthetic fatty acid may be used.
  • the fatty acid is totally or partially hydrogenated.
  • the fatty acid is purified.
  • the fatty acid used has a purity of at least 90 % by weight, more preferably at least 95 % by weight, still more preferably at least 99% by weight. Since most natural sources of fatty acids comprise a mixture of different acids, natural products are preferably purified prior to use.
  • R 1 is a linear or branched alkyl or alkenyl group containing from 5 to 23 carbon atoms, preferably containing from 9 to 21 carbon atoms, more preferably containing from 14 to 21 carbon atoms; and 0 to 3 double bonds, preferably 0 or 1 double bonds.
  • linear or branched alkyl or alkenyl groups are products obtained from oils and fats from plants and animals, such as palm, coconut, sunflower, soybean, palm olein, olive, canola, tall oil or tallow, possibly totally or partially hydrogenated and purified, or synthetic fatty acids such as palmitoleic acid, oleic acid, elaidinic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid, behenic acid and erucic acid or mixtures thereof.
  • palm and partially hydrogenated palm fatty acid are used.
  • C 8-24 fatty acids that may be used in the methods of the invention include palmitoleic acid, oleic acid, elaidinic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid, behenic acid and erucic acid, or mixtures thereof.
  • the reaction between the alkanolamine or akanolamine mixture and the compound of formula R 1 COOH, e.g. C 8-24 fatty acid, is an esterification and it may be conducted under conditions known in the art, e.g. as described in patent application ES-A-2021900 .
  • the compounds of the invention are, however, diesters thus preferably the esterification reaction is carried out under conditions that maximizes the yield of diester.
  • the ratio of compound of formula R 1 COOH or a derivative thereof, e.g. C 8-24 fatty acid, to the alkanolamine, e.g. triethanolamine, used in the esterification reaction is preferably lower than 2.5, more preferably between 1.2 and 2.5.
  • the esterification reaction is carried out in the presence of a catalyst such as hypophosphorous acid or paratoluenesulfonic acid.
  • a catalyst such as hypophosphorous acid or paratoluenesulfonic acid.
  • Conventional stabilizers and/or antioxidants such as tocopherols, BHT, BHA, citric acid, etc may also be present in the esterification reaction mixture.
  • the esterification reaction is carried out at a temperature between 120°C and 220°C.
  • the preferred reaction time is 2-10 hours.
  • the reaction is carried out a reduced pressure of about 5 to 200 mbar.
  • the progress of the reaction may be monitored using conventional techniques, e.g. TLC or HPLC.
  • the reaction may, for example, be monitored for consumption of compound of formula R 1 COOH.
  • the product may also contain some unreacted compound of formula R 1 COOH.
  • composition is also likely to comprise methylated alkanolamine, methylated triethanolamine when ethanolamine is used.
  • the present invention comprises one or more amidoamine compounds (b), wherein the one or more amidoamine compounds (b) preferably comprise at least an amidoamine compound of formula (II) or even more preferably the one or more amidoamine compounds (b) are all represented by formula (II): wherein R 1 represents a linear or branched, saturated or unsaturated alkyl chain group containing from 8 to 36 carbon atoms, R 2 represents a linear or branched alkylene group containing from 1 to 6 carbon atoms, and R 3 and R 4 each independently represent a linear or branched alkyl group containing 1 to 3 carbon atoms.
  • the one or more amidoamine compounds (b) are represented by formula (II), wherein R 1 preferably represents a linear or branched, saturated or unsaturated alkyl chain group having from 6 to 24 carbon atoms, more preferably from 12 to 24 carbon atoms; R 2 represents a linear or branched alkylene group containing preferably 3 carbon atoms, and R 3 and R 4 each independently represent preferably a methyl group.
  • the amidoamine compounds (b) is selected from the group consisting of lauramidopropyl dimethylamine, myristamidopropyl dimethylamine, palmitamidopropyl dimethylamine, behenamidopropyl dimethylamine, stearamidopropyl dimethylamine, oleamidopropyl dimethylamine, and mixtures thereof.
  • amidoamine compounds (b) is behenamidopropyldimethylamine.
  • the one or more amidoamine compounds (b) are generally obtained by the reaction of a fatty acid (natural origin or technical mixture of fatty acids) and dimethylaminopropylamine.
  • Behenamidopropyldimethylamine can be obtained from the reaction of a behenic acid (docosanoic acid) composition and dimethylamino propyl amine.
  • Behenic acid dimethylaminopropylamide conforms to formula (II') R-CO-NH (CH 2 ) 3 -N (CH 3 ) 2 (II') wherein R corresponds essentially to a C 21 alkyl group.
  • Behenic acid is preferably derived from natural fat and oil as well as synthetic triglycerides. Due to its possible natural origin, the fatty acid composition of behenic acid (i.e. the behenic acid composition) includes not only behenic acid, but also other fatty acids, such as small amounts of Palmitic Acid (C 16 ), Stearic Acid (C 18 ), Arachidic Acid (C 20 ), Lignoceric Acid (C 24 ) and others. Therefore, the content of behenic acid dimethylaminopropylamide, or a salt thereof, in the component b) is 60 wt.% or higher, preferably equal or higher than 75 wt.%. It is particularly preferred that the content of C 21 in R is equal or higher than 85 wt.% and the content of C 17 is lower than 5 wt.%
  • the salts of the behenic acid dimethylaminopropylamide are also possible use as compound b).
  • Said salts are obtained by neutralizing or partially neutralizing the behenic acid dimethylaminopropylamide with organic and/or inorganic acids, like hydrochloric acid, phosphoric acid, acetic acid, lactic acid, glycolic acid, malic acid, succinic acid, citric acid, L-glutamic acid, pyroglutamic acid, C 6 -C 22 fatty acids, like lauric acid, oleic acid, stearic acid and mixtures thereof, and alkyl ether carboxylic acids of formula R-O- (CH 2 CH 2 O) n -CH 2 COOH wherein R represents a C 2 -C 10 alkyl chain, preferably C 6 -C 8 alkyl, and n has a value in the range of 1 to 10, preferably 3-8.
  • amidoamines examples are those corresponding to the commercial reference AMIDET® APA-18, (INCI Stearamidopropyl Dimethylamine), and AMIDET® APA-22 (INCI Behenamidopropyl Dimethylamine), all of them marketed by KAO Chemicals Europe.
  • the present invention comprises one or more fatty alcohols (c), preferably the fatty alcohols (c) comprise fatty alcohols containing from 6 to 22 carbon atoms.
  • the C6-C22 fatty alcohols are aliphatic alcohols derived from natural fats and oils, as well as synthetic origin.
  • Preferred fats and oils include palm oil, coconut oil, sunflower oil, rapeseed oil, castor oil, olive oil, soybean oil; and animal fat such as tallow, bone oil; fish oil, hardened oils and semi hardened oils thereof; and mixtures thereof.
  • the C6-C22 fatty alcohols are ethoxylated and/or propoxylated, having an average alkoxylation degree from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10, most preferred from 2 to 8.
  • the fatty alcohols are not alkoxylated fatty alcohols.
  • C6-C22 fatty alcohols include capryl alcohol (1-octanol), pelargonic alcohol (1-nonanol), capric alcohol (1-decanol), lauryl alcohol (1-dodecanol), myristyl alcohol (1-tetradecanol), cetyl alcohol (1-hexadecanol), palmitoleyl alcohol (cis-9-hexadecan-1-ol), stearyl alcohol (1-octadecanol), isostearyl alcohol (16-methylheptadecan-1-ol), elaidyl alcohol (9E-octadecen-1-ol), oleyl alcohol (cis-9-octadecen-l-ol), linoleyl alcohol (9Z, 12Z-octadecadien-1-ol), elaidolinoleyl alcohol (9E, 12E-octadecadien-1-ol), linolenyl alcohol(9
  • Examples of commercially available fatty alcohols are those corresponding to the commercial reference KALCOL® 6098, (INCI Cetyl Alcohol, KALCOL® 8098 (INCI Stearyl Alcohol), KALCOL® 6850P, (INCI Cetearyl Alcohol), all of them marketed by KAO Chemicals Europe.
  • the main object of the present invention is a cosmetic composition, comprising:
  • the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is 1:3 and 3:1, more preferably 2:1.
  • the cosmetic composition comprises one or more quaternary ester ammonium compounds (a), behenamidopropyl dimethylamine (b), and one or more fatty alcohols (c), wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the behenamidopropyl dimethylamine (b) is within a range of 1:5 to 5:1.
  • the cosmetic composition according to the invention is a room temperature solid cosmetic composition, wherein the water content in the solid cosmetic composition is 10 wt.-% or less.
  • the cosmetic composition according to the invention is a room temperature solid cosmetic composition, wherein the water content in the solid cosmetic composition is 5 wt.-% or less, more preferably 3 wt.-% or less, most preferred 0.2 wt.-% wt or less.
  • the cosmetic composition comprises,
  • the cosmetic composition of the present invention can be prepared by mixing one or more quaternary ester ammonium compounds (a), one or more amidoamine compounds (b) and one or more fatty alcohols (c) at 80°C or 85°C with stirring until complete homogenization, and then the mixture is cooled down to room temperature, whereby a solid suitable for pelleting can be obtained.
  • the present invention further provides a hair conditioning composition comprising:
  • the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:3 and 3:1.
  • the molar ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:13 to 2:1, more preferably within the range of 1,26:1 to 1:8.
  • the molar ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is 1:1,25.
  • Another aspect of the invention is a method to obtain the hair conditioner composition of the present invention, said method comprises a step a) of dispersing the solid composition according to the present invention in water, wherein the method is carried at a temperature within a range of 15 to 40°C, preferably within a range of 18 to 35°C, more preferably within a range of 20 to 30°C, most preferably at room temperature.
  • composition obtained by the above method is suitable for use as a hair conditioner.
  • the use of the hair conditioner composition according to the invention or obtained according to the method as defined in the present invention for the conditioning treatment of hair is also part of the invention.
  • a method of conditioning human hair wherein the hair conditioner composition according to the present invention or obtained according to the method as defined in the present invention is applied to the hair and further rinsed from the hair with water, or alternatively is left on hair as leave-on conditioner, is also a part of the invention
  • the cosmetic composition and the hair conditioner composition according to the present invention may also comprise oil components, silicone compounds, powders, amphoteric surfactants, non-ionic surfactants, polymers, metal ion sequestering agents, UV protection factors, vitamins, antioxidants, antioxidant aids, perfume oils, germ inhibitors and the like as further auxiliaries and additives.
  • oils include liquid oils, solid oils, waxes, hydrocarbon oils and synthetic ester oils.
  • Suitable oil components are, for example, Guerbet alcohols based on fatty alcohols containing 6 to 22 and preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-C22 carboxylic acids with linear C6-C22 fatty alcohols such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate,
  • esters of linear C6-C22 fatty acids with branched alcohols are particularly 2-ethyl hexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C6-C10 fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-C18 fatty acids, esters of C6-C22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of C6-C12 dicarboxylic acids with linear or branched alcohols containing 1 to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils such as avocado oil, almond oil, ha
  • waxes examples include natural waxes such as, for example, candelilla wax, carnauba wax, Japan wax, espartograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes) such as for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxes and synthetic waxes such as, for example, polyalkylene waxes and polyethylene glycol waxes
  • natural waxes such as, for example, candelilla wax, carnauba wax, Japan wax, espartograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax
  • hydrocarbon oils examples include liquid paraffin, squalane, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.
  • Suitable silicone compounds are, for example, dimethyl polysiloxanes, methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds which may be both liquid and resin-like at room temperature.
  • Preferred silicone compounds are hydrophobic silicone oils, which are silicone oils which are soluble in paraffinic oil at 25°C.
  • Hydrophobic silicone oils to be used according to the present invention include both volatile and non-volatile silicone oils.
  • cyclic methyl siloxane having the formula ⁇ (CH3)2SiO ⁇ x in which x is 3-6, or short chain linear methyl siloxanes having the formula ((CH3) 2 SiO ⁇ (CH 3 ) 2 SiO ⁇ y Si(CH 3 ) 3 in which y is 0-5.
  • cyclic methyl siloxanes are hexamethylcyclotrisiloxanes (D3), a solid with a boiling point of 134°C and the formula ⁇ (Me2)SiO ⁇ 3 ; octamethylcyclotetrasiloxane (D4) with a boiling point of 176°C, a viscosity of 2.3 mm 2 /s, and the formula ⁇ (Me 2 )SiO ⁇ 4 ; decamethylcyclopentasiloxane (D5) (cyclomethicone) with a boiling point of 210°C, a viscosity of 3.87 mm 2 /s, and the formula ⁇ (Me 2 ) SiO ⁇ 5 ; and dodecamethylcyclohexasiloxane (DE) with a boiling point of 245°C, a viscosity of 6.62 mm 2 /s and the formula ⁇ (Me 2 )SiO ⁇ 6 .
  • DE dodecamethyl
  • Some suitable short linear methyl siloxane are hexamethyldisiloxane (MM) with a boiling point of 100°C, viscosity of 0-65 mm ⁇ 2>/s, and formula Me 3 SiOMe 3 ; octamethyltrisiloxane (MDM) with a boiling point of 152°C., viscosity of 1.04 mm 2 /s, and formula Me 3 SiOMe 2 SiOSiMe 3 ; decamethyltetrasiloxane (MD2M) with a boiling point of 194°C, viscosity of 1.53 mm 2 /s, and formula Me 3 SiO(MeSiO) 2 SiMe 3 ; dodecamethylpentasiloxane (MD3M) with a boiling point of 229°C, viscosity of 2.06 mm 2 /s, and formula Me 3 SiO(Me 2 SiO) 3 SiMe 3 ; tetradecamethylhexasiloxan
  • long chain linear siloxanes such as phenyltrimethicone, bis(phenylpropyl)dimethicone, dimethicone, and dimethiconol are also included.
  • powders include inorganic powders such as talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, lepidolite, biotite, vermiculite, bentonite, hectorite, laponite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, metallic soap (e.g., zinc myristate, calcium palimitate, and aluminum stearate), and boron nitride; organic powders such as polyamide resin powder (nylon powder), polyethylene powder, polymethylmethacrylate powder, polystyrene powder, styrene-acrylic acid copolymer
  • amphoteric surfactants include imidazoline type amphoteric surfactants such as sodium 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy)-2-sodium salt; betaine type surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethyl aminoacetate betaine, alkyl betaine, amidobetaine, and sulfobetaine.
  • imidazoline type amphoteric surfactants such as sodium 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy)-2-sodium salt
  • betaine type surfactants such as 2-heptadec
  • lipophilic nonionic surfactants include sorbitan fatty acid esters (such as sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, and diglycerol sorbitan tetra-2-ethylhexylate); glycerol or polyglycerol fatty acid esters (such as glycerol mono-cotton seed oil fatty acid ester, glycerol monoerucate, glycerol sesquioleate, glycerol monostearate, glycerol-a, ⁇ '-oleate pyroglutamate, and glycerol monostearate malate); propylene glycol fatty acid esters (such as propylene glycol mono
  • hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (such as POE-sorbitan monooleate, POE-sorbitan monostearate, and POE-sorbitan tetraoleate); POE sorbitol fatty acid esters (such as POE-sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitol pentaoleate, and POE-sorbitol monostearate); POE-glycerol fatty acid esters (such as POE-monooleates, POE-glycerol monostearate, POE-glycerol monoisostearate, and POE-glycerol triisostearate); POE-fatty acid esters (such as POE-distearate, POE-monodioleate, and ethylene glycol distearate); POE-alkyl ethers (such as POE-lauryl ether, POE-
  • Suitable cationic polymers are, for example, cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, for example, Luviquat (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides such as, for example, Lauryidimonium Hydroxypropyl Hydrolyzed Collagen, quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as, for example, Amodimethicone, copolymers of adipic acid and dimethylamino-hydroxypropyl diethylenetriamine (Cartaretine, Sandoz), copolymers of acrylic acid with dimethyl diallyl ammonium chloride, polyquaternium type
  • Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copolymers and esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyl trimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert.-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl, acetate copolymers, vinyl pyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and
  • UV protection factors include organic substances (light filters) which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet radiation and of releasing the energy absorbed in the form of longer-wave radiation, for example heat.
  • UV-B filters can be oil-soluble or water-soluble.
  • oil-soluble substances 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3-(4-methylbenzylidene)-camphor; 4-aminobenzoic acid derivatives, preferably 4-(dimethylamino)-benzoic acid-2-ethylhexyl ester, 4-(dimethylamino)-benzoic acid-2-octyl ester and 4-(dimethylamino)-benzoic acid
  • esters of cinnamic acid preferably 4-methoxycinnamic acid-2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl ester (Octocrylene); esters of salicylic acid, preferably salicylic acid-2-ethylhexyl ester, salicylic acid-4-isopropylbenzyl ester, salicylic acid homomethyl ester;derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzo-phenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di-2-ethylhexyl ester
  • Typical UV-A filters are, in particular, derivatives of benzoyl methane such as, for example 1-(4'-tert.butylphenyl)-3-(4'-methoxyphenyl)-propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoyl methane (Parsol 1789) or 1-phenyl-3-(4'-isopropylphenyl)-propane-1,3-dione.
  • benzoyl methane such as, for example 1-(4'-tert.butylphenyl)-3-(4'-methoxyphenyl)-propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoyl methane (Parsol 1789) or 1-phenyl-3-(4'-isopropylphenyl)-propane-1,3-dione.
  • the UV-A and UV-B filters may of course also be used in the form of mixtures.
  • insoluble pigments i.e. finely dispersed metal oxides or salts
  • suitable metal oxides are, in particular, zinc oxide and titanium dioxide and also oxides of iron, zirconium, silicon, manganese, aluminium and cerium and mixtures thereof.
  • Silicates (talcum), barium sulfate and zinc stearate may be used as salts.
  • the oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and more preferably from 15 to 30 nm. They may be spherical in shape although ellipsoidal particles or other non-spherical particles may also be used.
  • the pigments may also be surface-treated, i.e. hydrophilicized or hydrophobicized. Typical examples are coated titanium dioxides such as, for example, Titandioxid T 805 (Degussa) or Eusolex T2000 (Merck). Suitable hydrophobic coating materials are, above all, silicones and especially trialkoxyoctyl silanes or simethicones. So-called micro- or nanopigments are preferably used in sun protection products. Micronized zinc oxide is preferably used.
  • Secondary sun protection factors of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin.
  • suitable antioxidants are amino acids (for example glycine, histidine, tyrosine, tryptophane) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotinoids, carotenes (for example ⁇ -carotene, ⁇ -carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, liponic acid and derivatives thereof (for example dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (for example thioredoxine, glutathione, cyste
  • metal ion sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid 4Na salt, disodium edetate, trisodium edetate, tetrasorium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, and trisodium hydroxyethyl ethylenediamine triacetate.
  • vitamins examples include vitamins A, B1, B2, B6, C, and E and the derivatives thereof; pantothenic acid and the derivatives thereof; and biotin.
  • antioxidants include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters.
  • antioxidant aids include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, lactic acid, fumaric acid, cephalin, hexametaphosphates, phytic acid, and ethylenediaminetetraacetic acid.
  • Suitable perfume oils are mixtures of natural and synthetic fragrances.
  • Natural fragrances include the extracts of blossoms (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamon, costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type.
  • perfume compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert-butyl cyclohexylacetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • Ethers include, for example, benzyl ethyl ether while aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, filial and bourgeonal.
  • suitable ketones are the ionones, ⁇ -isomethylionone and methyl cedryl ketone.
  • Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol.
  • the hydrocarbons mainly include the terpenes and balsams. However, it is preferred to use mixtures of different perfume compounds which, together, produce an agreeable fragrance.
  • Other suitable perfume oils are essential oils of relatively low volatility which are mostly used as aroma components. Examples are sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavendin oil.
  • bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ -nexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavendin oil, clary oil, ⁇ -damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose
  • germ inhibitors are preservatives which act specifically against gram-positive bacteria such as, for example, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di-(4-chlorophenyl-biguanido)-hexane) or TCC (3,4,4'-trichlorocarbanilide).
  • Numerous perfumes and essential oils also have antimicrobial properties.
  • Typical examples are the active substances eugenol, menthol and thymol in clove, mint and thyme oil.
  • Table 1 shows the ingredients used to prepared solid compositions. The amounts for each component indicated in Table 1 are indicated in percentage of active weight of each ingredient, and were prepared following the general method.
  • Table 2 summarizes the physical properties of the compositions prepared in defined in Table 1.
  • Table 1 % A B C D E F G H C1 EQ HC 1 22,7 22,1 22,7 22,1 14, 6 14,2 14,7 14,2 - Cetyl Alcohol - - - - 36,7 35,7 36,8 35,7 - Stearyl Alcohol - - - - 36,7 35,7 36,8 35,7 - Cetearyl Alcohol (50:50) 68,0 66,5 68,2 66,5 - - - - 66,6 Behenamido propyldime thylamine 9,21 9,00 - - 11,8 11,5 - - - Stereamido propyldime thylamine - - 8,98 8,75 - - 11,6 11,2 13,4 Lactic Acid 90% - 2,31 - 2,57 - 2,71 - 3,03 3,22 Behentrimo nium Chloride - - - - -
  • Hygroscopicity was measured by storing the sample at 20°C and 80% relative humidity and weighting the sample after specific times under these conditions.
  • Hardness was indirectly measured by penetrability by using a penetrometer (Normatest). The higher the penetrability the lower the hardness of the sample is.
  • compositions comprising Behenamidopropyl Dimethylamine, i.e. samples A, B, E and F, are preferred. Not neutralized samples (A and E) are even more preferred.
  • compositions described above (1,5% active cationic (esterquat and amidoamine) and 3% fatty alcohol) in water for 2 hours at 25°C at 250 rpm. Then samples were filtered by an ASTM 50 filter (300 micron) under pressure. The residue left on the filter was then dried for 24 hours at 50°C and weighted. Only compositions A, B, E and F were possible to filter completely. Thus, these composition are preferred having regard to the present invention.
  • Combing force reduction is one of the advantageous characteristics of the composition, as it is a measure of a good performance.
  • Combing forces were determined using a dynamometer (Instron 5543, cell 1 kg, rate 500 mm/min).
  • a Caucasian damaged hair tress of approximately 20 g and 22 cm in length was combed 10 times under wet and dry conditions and the values obtained were averaged.
  • compositions according to the invention have very low combing forces.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Emergency Medicine (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)

Abstract

The present invention relates to a composition comprising one or more quaternary ester ammonium compounds (a), one or more amidoamine compounds (b), wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:5 to 5:1, and one or more fatty alcohols (c). The present invention also relates to a composition that is solid at room temperature, to a hair conditioner composition and to a method to prepare the hair conditioner composition by dispersing the solid composition in water at moderate temperatures.

Description

    FIELD OF THE INVENTION
  • The present invention relates to a composition (hereafter also referred to as a cosmetic composition) comprising one or more quaternary ester ammonium compounds, one or more amidoamine compounds and one or more fatty alcohols. Also, the present invention relates to cosmetic compositions being solid at room temperature, and to a liquid hair conditioner composition that can be prepared from that solid cosmetic compositions, and a method to prepare a liquid hair conditioner composition by dispersing said solid cosmetic composition in water at moderate temperatures.
  • STATE OF THE ART
  • Human hair can become soiled from the contact with environment and from sebum secreted by the scalp. This soiling may cause the hair to have a dirty or greasy feel, and an unattractive appearance.
  • Shampooing cleans the hair by removing the excess of soil and sebum. However, shampooing can leave the hair in a wet, tangled and generally unmanageable state. Once the hair dries, it is often left in a dry, rough, lusterless or frizzy condition due to the removal of the hair's natural oils and other natural conditioning and moisturizing components. It can be also left with increased levels of static upon drying which can interfere with combing, brushing and styling of hair. Hair conditioning compositions are widely known and are typically applied to the hair immediately after shampooing and rinsing the hair to avoid the problems described above and provides conditioning effect to the hair. The conditioning composition is worked through the hair, and may be then used as a leave-on conditioner or it can be rinsed from the hair with water.
  • Traditionally, hair conditioning compositions have used cationic surfactants. Cationic surfactants are those in which the surfactant activity resides in the positively charged cation portion of the molecule. The cationic surfactants are therefore attracted to the negatively charged hair surface and deposited on the hair. Among cationic surfactants, quaternary ammonium compounds and alkyl amidoamine compounds are particularly suited to the treatment of human hair. Thus, many hair conditioning products are based on quaternary ammonium compounds and alkyl amidoamine compounds.
  • An important requirement for hair conditioning compositions is a good performance even for damaged hair. It has been found that certain a combination of certain quaternary ester ammonium compound and certain alkyl amidoamine, provides a good performance in terms of combing force and antistatic effect especially for damaged hair.
  • Another requirement for hair conditioner products is low energy consumption during the preparation of said compositions. This aspect relates to the fact that hair conditioner compositions found in the market are liquid preparations while some of the cationic surfactants used as ingredients of said preparations are solid at room temperature and not dispersible in water at room temperature; even when previously melted, in order the cationics are dispersed in water it is need water temperature at least of 50-60°C. This is the case for alkylamidoamines. In order to disperse them in water it is needed or using water a temperature around 80°C or melt the amidoamine an disperse it in water heated at around 60°C. The need of a melting step together with the need of using hot water involves energy consumption.
  • A way to eliminate the need of a melting step and simplify the hair conditioner preparation process is having a solid cosmetic composition which comprises one or more quaternary compounds as ingredient while being easily dispersible in water at moderate temperatures or even room temperature.
  • It is known in the prior art that the combination of certain quaternary ester ammonium compounds and certain alkyl amidoamine compounds at certain ratios, in addition of providing an advantageous performance with regard to the conditioning effect onto damaged hair, can be formulated with one or more fatty alcohols, to obtain a solid compound that can be easily dispersed in water at room temperature, being said dispersion suitable to obtain a good performing liquid hair conditioner.
  • Indeed, the combination of quaternary ester ammonium compounds and amidoamine is well known in the prior art. EP0786250 describes an aqueous formulation for conditioning hair comprising an active substance mixture comprising quaternary ammonium compounds (0.01-30%wt) and alkyl amidoamine compounds (0.01-30% wt) in addition to standard components. The treatment of human hair with the disclosed compositions lead to a good wet and dry combing advantageous coupled with good hair maintenance and low tendency to static electricity.
  • US20040146478 describes the use of mixtures comprising quaternary ammonium compounds and fatty acid amidoamine compounds for cosmetic preparations, especially for hair conditioner preparations, preferably in an emulsion form. The problem addressed was to provide transparent cosmetic preparations, more especially for hair care and particularly for conditioning the hair, which would allow the storage- and temperature-stable incorporation both of silicone oils and of antidandruff agent.
  • EP2394632 describes a hair conditioner composition being a solid or paste form at ambient temperature, aimed to provide an easily-handled hair conditioning composition with a very low water content and a low energy method of producing the same. The composition disclosed comprises a component (a) including higher alcohol with 16 carbon atoms or more, higher fatty acid with 16 carbon atoms or more and/or their derivatives, a component (b) being a cationic surfactant and a component (c) including polyhydric alcohol and/or polyethylene glycol having a melting point of 70°C or less.
  • To conclude, it is clear to the inventors that there is still a need for better compositions. Thus, it is an object of the present invention to provide a composition that provides very good performance, particularly in terms of combing force and/or antistatic effect, especially advantageous for damaged hair, wherein the composition comprises quaternary ester ammonium compounds and alkyl amidoamine compounds in certain ratios, together in combination with fatty alcohols. Another object of the present invention is to provide a composition that is solid at room temperature. Another object of the present invention is to provide a hair conditioner composition and a method to prepare a hair conditioner composition by dispersing the solid composition according to the invention in water at moderate temperatures, thus obtaining a liquid hair conditioner.
  • SUMMARY OF THE INVENTION
  • According to the first aspect, the present invention provides a composition, said composition comprising:
    • one or more quaternary ester ammonium compounds (a),
    • one or more amidoamine compounds (b),
    • one or more fatty alcohols (c),
    wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:5 to 5:1.
  • The composition is generally a cosmetic composition or a composition used for the manufacture of a cosmetic composition.
  • According to the second aspect, the present invention provides a room temperature solid cosmetic composition, said composition comprising:
    • one or more quaternary ester ammonium compounds (a),
    • one or more amidoamine compounds (b),
    • one or more fatty alcohols (c),
    wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:5 to 5:1, and wherein the water content in the solid cosmetic composition is 10 wt.-% or less.
  • According to the third aspect, the present invention provides a hair conditioner composition comprising:
    • one or more quaternary ester ammonium compounds (a),
    • one or more amidoamine compounds (b),
    • one or more fatty alcohols (c),
    wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:5 to 5:1, and wherein the water content in the hair conditioner composition is more than 10 wt.-%.
  • According to the fourth aspect, the present invention provides a method to prepare a hair conditioner composition by dispersing the solid cosmetic composition according to the second aspect of the present invention in water at a temperature within a range of 15°C to 40°C, preferably within a range of 18 to 35°C, more preferably within a range of 20 to 30°C, most preferably at room temperature.
  • According to the fifth aspect, the present invention provides a use of the hair conditioner composition according to the third aspect of the present invention or obtained according to the fourth aspect of the present invention for the conditioning treatment of hair.
  • DETAILED DESCRIPTION OF THE INVENTION
  • In the present invention, room temperature is understood as a temperature in the range of 20°C to 25°C.
  • All percentages are weight percentages, unless otherwise indicated. Active weight is the weight of the active matter with respect to the total weight of the composition, wherein by active matter it is understood the set of specific components responsible for a certain action. In the scope of the present application (i.e. with reference to the composition) the active matter is the totality of ingredients, from which are derived all or part of its effectiveness, particularly components (a), (b), and (c).
  • The main object of the present invention is a composition comprising:
    • one or more quaternary ester ammonium compounds (a),
    • one or more amidoamine compounds (b),
    • one or more fatty alcohols (c),
    wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:5 to 5:1.
  • In a preferred embodiment of the present invention, the one or more amidoamine compounds (b) is behenamidopropyl dimethylamine.
  • Quaternary ester ammonium compound (a)
  • The present invention comprises one or more quaternary ester ammonium compounds (a), commonly known as esterquat, wherein the one or more quaternary ester ammonium compounds (a) preferably comprise at least a compound of formula (I) or even more preferably the one or more quaternary ester ammonium compounds (a) are all represented by formula (I) :
    Figure imgb0001
    wherein
    X1 represents an hydroxyalkyl group containing 1 to 4 carbon atoms or an alkyl group containing 1 to 4 carbon atoms or an alkyl group containing one aromatic group, preferably X1 is an alkyl group containing 1 to 4 carbon atoms, more preferably X1 is a methyl group;
    R1 is a linear or branched alkyl or alkenyl group containing from 5 to 23 carbon atoms and from 0 to 3 double bonds,
    R2 and R3 each independently represent H, OH or -O-Lq-C(O)-R1,
    L represents a -(OCH2CH2)a-(OR4CHCH2)b- group, wherein R4 represents an alkyl group containing 1-4 carbon atoms, a represents an average number within the range of 0 to 20, b represents an average number within the range of 0 to 6, and the sum of a+b represents an average number within the range of 0 to 26, preferably from 0 to 10, more preferably from 0 to 6, most preferred 0,
    q represents an average number within the range of 0 to 26,
    m, n, and p each independently represent an average number within the range of 1 to 4, and
    A represents an anion.
  • In a preferred embodiment of the invention the quaternary ammonium compound of the invention are preferably non-ethoxylated, non-propoxylated.
  • In a preferred embodiment m, n, and p are equal to 2. In another preferred embodiment m and p are equal to 2 and n is equal to 1.
  • Also in a preferred embodiment, q represents an average number within the range of 0 to 10, more preferably within the range of 0 to 6, most preferred 0.
  • A preferably represents an halide, phosphate or alkylsulphate, more preferably an alkylsulphate, most preferred methylsulphate.
  • In preferred embodiments where q is not 0, and a+b is not 0, the quaternary ester ammonium compound of the invention is an ethoxylated and/or propoxylated esterquat. The order of sequence of the ethylene oxide and propylene oxide groups is not critical for the invention.
  • In one embodiment of the present invention, the one or more quaternary ester ammonium compounds (a) of formula (I) comprises a mixture of at least one or more mono-quaternary ester ammonium compounds, di-quaternary ester ammonium compounds or tri-quaternary ester ammonium compounds of formula (I.1), (I.2) and (I.3).
    Figure imgb0002
    Figure imgb0003
    Figure imgb0004
    wherein in formula I.1, I.2 and I.3
    R2 and R3 each independently represent -H, or -OH,
    X1 represents an hydroxyalkyl group containing 1 to 4 carbon atoms or an alkyl group containing 1 to 4 carbon atoms or an alkyl group containing one aromatic group, preferably X1 is an alkyl group containing 1 to 4 carbon atoms, more preferably X1 is a methyl group;
    R1 is a linear or branched alkyl or alkenyl group containing from 5 to 23 carbon atoms and from 0 to 3 double bonds,
    L represents a -(OCH2CH2)a-(OR4CHCH2)b- group, wherein R4 represents an alkyl group containing 1-4 carbon atoms, a represents an average number within the range of 0 to 20, b represents an average number within the range of 0 to 6, and the sum of a+b represents an average number within the range of 0 to 26, preferably from 0 to 10, more preferably from 0 to 6, most preferred 0,
    q represents an average number within the range of 0 to 26,
    m, n, and p each independently represent an average number within the range of 1 to 4, and
    A represents an anion.
  • In another embodiment of the present invention, the one or more quaternary ester ammonium compounds (a) are obtained from triethanolamine or methyldiethanolamine or mixtures thereof, preferably from triethanolamine.
  • In particularly preferred methods of the invention, the compound of formula (I) is prepared by reacting triethanolamine or methyldiethanoalime or mixtures thereof, preferably triethanolamine, with a compound of formula R1COOH or a derivative thereof (e.g. a chloride, anhydride or ester thereof) wherein R' is as hereinbefore defined.
  • Preferably the compound of formula R1COOH is a C8-24 fatty acid. The fatty acid may be a natural product obtained from the oils and fats of plants and animals, such as palm, sunflower, soybean, olive, canola, tallow and tall oil. Alternatively a synthetic fatty acid may be used. Optionally the fatty acid is totally or partially hydrogenated. Optionally the fatty acid is purified. Preferably the fatty acid used has a purity of at least 90 % by weight, more preferably at least 95 % by weight, still more preferably at least 99% by weight. Since most natural sources of fatty acids comprise a mixture of different acids, natural products are preferably purified prior to use.
  • In one embodiment of the present invention, R1 is a linear or branched alkyl or alkenyl group containing from 5 to 23 carbon atoms, preferably containing from 9 to 21 carbon atoms, more preferably containing from 14 to 21 carbon atoms; and 0 to 3 double bonds, preferably 0 or 1 double bonds.
    Examples of linear or branched alkyl or alkenyl groups are products obtained from oils and fats from plants and animals, such as palm, coconut, sunflower, soybean, palm olein, olive, canola, tall oil or tallow, possibly totally or partially hydrogenated and purified, or synthetic fatty acids such as palmitoleic acid, oleic acid, elaidinic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid, behenic acid and erucic acid or mixtures thereof. Preferably palm and partially hydrogenated palm fatty acid are used.
  • Representative examples of C8-24 fatty acids that may be used in the methods of the invention include palmitoleic acid, oleic acid, elaidinic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid, behenic acid and erucic acid, or mixtures thereof.
  • The reaction between the alkanolamine or akanolamine mixture and the compound of formula R1COOH, e.g. C8-24 fatty acid, is an esterification and it may be conducted under conditions known in the art, e.g. as described in patent application ES-A-2021900 . The compounds of the invention are, however, diesters thus preferably the esterification reaction is carried out under conditions that maximizes the yield of diester.
  • The ratio of compound of formula R1COOH or a derivative thereof, e.g. C8-24 fatty acid, to the alkanolamine, e.g. triethanolamine, used in the esterification reaction is preferably lower than 2.5, more preferably between 1.2 and 2.5. Preferably the esterification reaction is carried out in the presence of a catalyst such as hypophosphorous acid or paratoluenesulfonic acid. Conventional stabilizers and/or antioxidants such as tocopherols, BHT, BHA, citric acid, etc may also be present in the esterification reaction mixture.
  • Preferably the esterification reaction is carried out at a temperature between 120°C and 220°C. The preferred reaction time is 2-10 hours. Preferably the reaction is carried out a reduced pressure of about 5 to 200 mbar. The progress of the reaction may be monitored using conventional techniques, e.g. TLC or HPLC. The reaction may, for example, be monitored for consumption of compound of formula R1COOH.
  • The product may also contain some unreacted compound of formula R1COOH.
  • The composition is also likely to comprise methylated alkanolamine, methylated triethanolamine when ethanolamine is used.
  • Amidoamine compounds (b)
  • The present invention comprises one or more amidoamine compounds (b), wherein the one or more amidoamine compounds (b) preferably comprise at least an amidoamine compound of formula (II) or even more preferably the one or more amidoamine compounds (b) are all represented by formula (II):
    Figure imgb0005
    wherein
    R1 represents a linear or branched, saturated or unsaturated alkyl chain group containing from 8 to 36 carbon atoms,
    R2 represents a linear or branched alkylene group containing from 1 to 6 carbon atoms, and
    R3 and R4 each independently represent a linear or branched alkyl group containing 1 to 3 carbon atoms.
  • In one embodiment of the present invention, the one or more amidoamine compounds (b) are represented by formula (II), wherein R1 preferably represents a linear or branched, saturated or unsaturated alkyl chain group having from 6 to 24 carbon atoms, more preferably from 12 to 24 carbon atoms; R2 represents a linear or branched alkylene group containing preferably 3 carbon atoms, and R3 and R4 each independently represent preferably a methyl group.
  • In another embodiment of the present invention, the amidoamine compounds (b) is selected from the group consisting of lauramidopropyl dimethylamine, myristamidopropyl dimethylamine, palmitamidopropyl dimethylamine, behenamidopropyl dimethylamine, stearamidopropyl dimethylamine, oleamidopropyl dimethylamine, and mixtures thereof.
  • In a specially preferred embodiment of the invention the amidoamine compounds (b) is behenamidopropyldimethylamine.
  • The one or more amidoamine compounds (b) are generally obtained by the reaction of a fatty acid (natural origin or technical mixture of fatty acids) and dimethylaminopropylamine.
  • Behenamidopropyldimethylamine can be obtained from the reaction of a behenic acid (docosanoic acid) composition and dimethylamino propyl amine.
  • Behenic acid dimethylaminopropylamide conforms to formula (II')

             R-CO-NH (CH2)3-N (CH3)2     (II')

    wherein R corresponds essentially to a C21 alkyl group.
  • Behenic acid is preferably derived from natural fat and oil as well as synthetic triglycerides. Due to its possible natural origin, the fatty acid composition of behenic acid (i.e. the behenic acid composition) includes not only behenic acid, but also other fatty acids, such as small amounts of Palmitic Acid (C16), Stearic Acid (C18), Arachidic Acid (C20), Lignoceric Acid (C24) and others. Therefore, the content of behenic acid dimethylaminopropylamide, or a salt thereof, in the component b) is 60 wt.% or higher, preferably equal or higher than 75 wt.%. It is particularly preferred that the content of C21 in R is equal or higher than 85 wt.% and the content of C17 is lower than 5 wt.%
  • According to the invention, the salts of the behenic acid dimethylaminopropylamide are also possible use as compound b). Said salts are obtained by neutralizing or partially neutralizing the behenic acid dimethylaminopropylamide with organic and/or inorganic acids, like hydrochloric acid, phosphoric acid, acetic acid, lactic acid, glycolic acid, malic acid, succinic acid, citric acid, L-glutamic acid, pyroglutamic acid, C6-C22 fatty acids, like lauric acid, oleic acid, stearic acid and mixtures thereof, and alkyl ether carboxylic acids of formula

             R-O- (CH2CH2O)n-CH2COOH

    wherein R represents a C2-C10 alkyl chain, preferably C6-C8 alkyl, and n has a value in the range of 1 to 10, preferably 3-8.
    Examples of commercially available amidoamines are those corresponding to the commercial reference AMIDET® APA-18, (INCI Stearamidopropyl Dimethylamine), and AMIDET® APA-22 (INCI Behenamidopropyl Dimethylamine), all of them marketed by KAO Chemicals Europe.
  • Fatty alcohols (c)
  • The present invention comprises one or more fatty alcohols (c), preferably the fatty alcohols (c) comprise fatty alcohols containing from 6 to 22 carbon atoms.
  • The C6-C22 fatty alcohols are aliphatic alcohols derived from natural fats and oils, as well as synthetic origin. Preferred fats and oils include palm oil, coconut oil, sunflower oil, rapeseed oil, castor oil, olive oil, soybean oil; and animal fat such as tallow, bone oil; fish oil, hardened oils and semi hardened oils thereof; and mixtures thereof.
  • Optionally, the C6-C22 fatty alcohols are ethoxylated and/or propoxylated, having an average alkoxylation degree from 1 to 30, preferably from 1 to 20, more preferably from 1 to 10, most preferred from 2 to 8.
  • In a preferred embodiment the fatty alcohols are not alkoxylated fatty alcohols.
  • Examples of C6-C22 fatty alcohols include capryl alcohol (1-octanol), pelargonic alcohol (1-nonanol), capric alcohol (1-decanol), lauryl alcohol (1-dodecanol), myristyl alcohol (1-tetradecanol), cetyl alcohol (1-hexadecanol), palmitoleyl alcohol (cis-9-hexadecan-1-ol), stearyl alcohol (1-octadecanol), isostearyl alcohol (16-methylheptadecan-1-ol), elaidyl alcohol (9E-octadecen-1-ol), oleyl alcohol (cis-9-octadecen-l-ol), linoleyl alcohol (9Z, 12Z-octadecadien-1-ol), elaidolinoleyl alcohol (9E, 12E-octadecadien-1-ol), linolenyl alcohol(9Z,12Z,15Z-octadecatrien-1-ol), elaidolinolenyl alcohol (9E, 12E, 15-E-octadecatrien-1-ol), ricinoleyl alcohol (12-hydroxy-9-octadecen-1-ol), arachidyl alcohol (1-eicosanol), behenyl alcohol (1-docosanol), erucyl alcohol (cis-13-docosen-1-ol, and mixtures thereof.
  • Examples of commercially available fatty alcohols are those corresponding to the commercial reference KALCOL® 6098, (INCI Cetyl Alcohol, KALCOL® 8098 (INCI Stearyl Alcohol), KALCOL® 6850P, (INCI Cetearyl Alcohol), all of them marketed by KAO Chemicals Europe.
  • Cosmetic composition of the invention
  • The main object of the present invention is a cosmetic composition, comprising:
    • one or more quaternary ester ammonium compounds (a),
    • one or more amidoamine compounds (b),
    • one or more fatty alcohols (c),
    wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:5 to 5:1.
  • In a preferred embodiment of the present invention, the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is 1:3 and 3:1, more preferably 2:1.
  • In a specially preferred embodiment of the present invention, the cosmetic composition comprises one or more quaternary ester ammonium compounds (a), behenamidopropyl dimethylamine (b), and one or more fatty alcohols (c), wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the behenamidopropyl dimethylamine (b) is within a range of 1:5 to 5:1.
  • In another preferred embodiment of the present invention, the cosmetic composition according to the invention is a room temperature solid cosmetic composition, wherein the water content in the solid cosmetic composition is 10 wt.-% or less.
  • In a further preferred embodiment, the cosmetic composition according to the invention is a room temperature solid cosmetic composition, wherein the water content in the solid cosmetic composition is 5 wt.-% or less, more preferably 3 wt.-% or less, most preferred 0.2 wt.-% wt or less.
  • In another embodiment of the present invention, the cosmetic composition comprises,
    • 2.5% to 42%, preferably 13% to 25%, more preferably 20% to 24%, of the one or more quaternary ester ammonium compounds (a),
    • 2.5% to 42%, preferably 6% to 25%, more preferably 7% to 15%, of the one or more amidoamine compounds (b),
    • 50% to 83%, preferably 60% to 75%, more preferably 65% to 70%, of the one or more fatty alcohols (c),
    wherein the amounts indicated are expressed as percentage by active weight (with respect to the total weight of the composition).
  • The cosmetic composition of the present invention can be prepared by mixing one or more quaternary ester ammonium compounds (a), one or more amidoamine compounds (b) and one or more fatty alcohols (c) at 80°C or 85°C with stirring until complete homogenization, and then the mixture is cooled down to room temperature, whereby a solid suitable for pelleting can be obtained.
  • Hair conditioner composition:
  • The present invention further provides a hair conditioning composition comprising:
    • one or more quaternary ester ammonium compounds (a),
    • one or more amidoamine compounds (b),
    • one or more fatty alcohols (c),
    wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:5 to 5:1, and wherein the water content in the hair conditioner composition is more than 10 wt.-%, preferably more than 30 wt%, more preferably more than 50 wt%, even more preferably more than 80 wt%, even more preferred more than 90 wt%, most preferred higher than 95 wt%.
  • In a preferred embodiment of the present invention, the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:3 and 3:1.
  • In another preferred embodiment of the present invention, the molar ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:13 to 2:1, more preferably within the range of 1,26:1 to 1:8.
  • In a specially preferred embodiment of the present invention, the molar ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is 1:1,25.
  • Another aspect of the invention is a method to obtain the hair conditioner composition of the present invention, said method comprises a step a) of dispersing the solid composition according to the present invention in water, wherein the method is carried at a temperature within a range of 15 to 40°C, preferably within a range of 18 to 35°C, more preferably within a range of 20 to 30°C, most preferably at room temperature.
  • The composition obtained by the above method is suitable for use as a hair conditioner. Thus, the use of the hair conditioner composition according to the invention or obtained according to the method as defined in the present invention for the conditioning treatment of hair is also part of the invention.
  • A method of conditioning human hair, wherein the hair conditioner composition according to the present invention or obtained according to the method as defined in the present invention is applied to the hair and further rinsed from the hair with water, or alternatively is left on hair as leave-on conditioner, is also a part of the invention
  • The cosmetic composition and the hair conditioner composition according to the present invention may also comprise oil components, silicone compounds, powders, amphoteric surfactants, non-ionic surfactants, polymers, metal ion sequestering agents, UV protection factors, vitamins, antioxidants, antioxidant aids, perfume oils, germ inhibitors and the like as further auxiliaries and additives.
  • Examples of oils include liquid oils, solid oils, waxes, hydrocarbon oils and synthetic ester oils. Suitable oil components are, for example, Guerbet alcohols based on fatty alcohols containing 6 to 22 and preferably 8 to 10 carbon atoms, esters of linear C6-C22 fatty acids with linear C6-C22 fatty alcohols, esters of branched C6-C22 carboxylic acids with linear C6-C22 fatty alcohols such as, for example, myristyl myristate, myristyl palmitate, myristyl stearate, myristyl isostearate, myristyl oleate, myristyl behenate, myristyl erucate, cetyl myristate, cetyl palmitate, cetyl stearate, cetyl isostearate, cetyl oleate, cetyl behenate, cetyl erucate, stearyl myristate, stearyl palmitate, stearyl stearate, stearyl isostearate, stearyl oleate, stearyl behenate, stearyl erucate, isostearyl myristate, isopropyl myristate, isostearyl palmitate, isostearyl stearate, isostearyl isostearate, isostearyl oleate, isostearyl behenate, isostearyl oleate, oleyl myristate, oleyl palmitate, oleyl stearate, oleyl isostearate, oleyl oleate, oleyl behenate, oleyl erucate, behenyl myristate, behenyl palmitate, behenyl stearate, behenyl isostearate, behenyl oleate, behenyl behenate, behenyl erucate, erucyl myristate, erucyl palmitate, erucyl stearate, erucyl isostearate, erucyl cleats, erucyl behenate and erucyl erucate. Also suitable are esters of linear C6-C22 fatty acids with branched alcohols, more particularly 2-ethyl hexanol, esters of hydroxycarboxylic acids with linear or branched C6-C22 fatty alcohols, esters of linear and/or branched fatty acids with polyhydric alcohols for example propylene glycol, dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides based on C6-C10 fatty acids, liquid mono-/di-/triglyceride mixtures based on C6-C18 fatty acids, esters of C6-C22 fatty alcohols and/or Guerbet alcohols with aromatic carboxylic acids, more particularly benzoic acid, esters of C6-C12 dicarboxylic acids with linear or branched alcohols containing 1 to 22 carbon atoms or polyols containing 2 to 10 carbon atoms and 2 to 6 hydroxyl groups, vegetable oils such as avocado oil, almond oil, hazelnut oil, babassu palm oil, borage oil, peanut oil, jojoba oil, canola oil, hemp oil, soybean oil, milk thistle oil, safflower oil, chufa oil, coconut oil, rapeseed oil, black cumin oil, wheat germ oil, sunflower oil, linseed oil, macadamia nut oil, corn oil, walnut oil, olive oil, branched primary alcohols, substituted cyclohexanes, linear and branched C6-C22 fatty alcohol carbonates, Guerbet carbonates, esters of benzoic acid with linear and/or branched C6-C22 alcohols, linear or branched, symmetrical or non-symmetrical dialkyl ethers containing 6 to 22 carbon atoms per alkyl group, ring opening products of epoxidized fatty acid esters with polyols, silicone oils and/or aliphatic or naphthenic hydrocarbons, for example dialkyl cyclohexanes. Examples of waxes include natural waxes such as, for example, candelilla wax, carnauba wax, Japan wax, espartograss wax, cork wax, guaruma wax, rice oil wax, sugar cane wax, ouricury wax, montan wax, beeswax, shellac wax, spermaceti, lanolin (wool wax), uropygial fat, ceresine, ozocerite (earth wax), petrolatum, paraffin waxes, microwaxes; chemically modified waxes (hard waxes) such as for example, montan ester waxes, sasol waxes, hydrogenated jojoba waxes and synthetic waxes such as, for example, polyalkylene waxes and polyethylene glycol waxes
  • Examples of hydrocarbon oils include liquid paraffin, squalane, pristane, paraffin, ceresin, squalene, petrolatum, and microcrystalline wax.
  • Suitable silicone compounds are, for example, dimethyl polysiloxanes, methylphenyl polysiloxanes, cyclic silicones and amino-, fatty acid-, alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/or alkyl-modified silicone compounds which may be both liquid and resin-like at room temperature. Preferred silicone compounds are hydrophobic silicone oils, which are silicone oils which are soluble in paraffinic oil at 25°C. Hydrophobic silicone oils to be used according to the present invention include both volatile and non-volatile silicone oils.
  • Specific examples include a cyclic methyl siloxane having the formula {(CH3)2SiO}x in which x is 3-6, or short chain linear methyl siloxanes having the formula ((CH3)2SiO{(CH3)2SiO}ySi(CH3)3 in which y is 0-5.
  • Some suitable cyclic methyl siloxanes are hexamethylcyclotrisiloxanes (D3), a solid with a boiling point of 134°C and the formula {(Me2)SiO}3; octamethylcyclotetrasiloxane (D4) with a boiling point of 176°C, a viscosity of 2.3 mm2/s, and the formula {(Me2)SiO}4; decamethylcyclopentasiloxane (D5) (cyclomethicone) with a boiling point of 210°C, a viscosity of 3.87 mm2/s, and the formula {(Me2) SiO}5; and dodecamethylcyclohexasiloxane (DE) with a boiling point of 245°C, a viscosity of 6.62 mm2/s and the formula {(Me2)SiO}6.
  • Some suitable short linear methyl siloxane are hexamethyldisiloxane (MM) with a boiling point of 100°C, viscosity of 0-65 mm<2>/s, and formula Me3SiOMe3; octamethyltrisiloxane (MDM) with a boiling point of 152°C., viscosity of 1.04 mm2/s, and formula Me3SiOMe2SiOSiMe3; decamethyltetrasiloxane (MD2M) with a boiling point of 194°C, viscosity of 1.53 mm2/s, and formula Me3SiO(MeSiO)2SiMe3; dodecamethylpentasiloxane (MD3M) with a boiling point of 229°C, viscosity of 2.06 mm2/s, and formula Me3SiO(Me2SiO)3SiMe3; tetradecamethylhexasiloxane (MD4M) with a boiling point of 245°C, viscosity of 2.63 mm2/s, and formula Me3SiO(Me2SiO)4SiMe3; and hexadecamethylheptasiloxane (MD5M) with a boiling point of 270°C, viscosity of 3.24 mm2/s, and formula Me3SiO(Me2SiO)5SiMe3.
  • Furthermore, long chain linear siloxanes such as phenyltrimethicone, bis(phenylpropyl)dimethicone, dimethicone, and dimethiconol are also included.
  • Examples of powders include inorganic powders such as talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, lepidolite, biotite, vermiculite, bentonite, hectorite, laponite, magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, metallic soap (e.g., zinc myristate, calcium palimitate, and aluminum stearate), and boron nitride; organic powders such as polyamide resin powder (nylon powder), polyethylene powder, polymethylmethacrylate powder, polystyrene powder, styrene-acrylic acid copolymer resin powder, benzoguanamine resin powder, poly(tetrafluroethylene) powder, and cellulose powder; inorganic white pigments such as titanium dioxide and zinc oxide; inorganic red pigments such as iron oxide (red iron oxide) and iron titanate; inorganic brown pigments such as γ-iron oxide; inorganic yellow pigments such as yellow iron oxide and ocher; inorganic black pigments such as black iron oxide and lower order titanium oxide; inorganic purple pigments such as mango violet and cobalt violet; inorganic green pigments such as chrome oxide, chrome hydroxide, and cobalt titanate; inorganic blue pigments such as ultramarine and Prussian blue; pearl pigments such as titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, and fish scale flakes; metal powder pigments such as aluminum powder and copper powder; organic pigments such as zirconium, barium, or aluminum lake (e.g., organic pigments such as Red No.201, Red No.202, Red No.204, Red No.205, Red No.220, Red No.226, Red No.228, Red No.405, Orange No.203, Orange No.204, Yellow No.205, Yellow No.401, and Blue No.404,or Red No.3, Red No.104, Red No.106, Red No.227, Red No.230, Red No.401, Red No.505, Orange No.205, Yellow No.4, Yellow No.5, Yellow No.202, Yellow No.203, Green No.3, and Blue No.1); and natural colors such as chlorophyll and β-carotene.
  • Examples of amphoteric surfactants include imidazoline type amphoteric surfactants such as sodium 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy)-2-sodium salt; betaine type surfactants such as 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethyl aminoacetate betaine, alkyl betaine, amidobetaine, and sulfobetaine.
  • Examples of lipophilic nonionic surfactants include sorbitan fatty acid esters (such as sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, and diglycerol sorbitan tetra-2-ethylhexylate); glycerol or polyglycerol fatty acid esters (such as glycerol mono-cotton seed oil fatty acid ester, glycerol monoerucate, glycerol sesquioleate, glycerol monostearate, glycerol-a, α'-oleate pyroglutamate, and glycerol monostearate malate); propylene glycol fatty acid esters (such as propylene glycol monostearate); hardened castor oil derivatives; and glycerol alkyl ethers.
  • Examples of hydrophilic nonionic surfactants include POE-sorbitan fatty acid esters (such as POE-sorbitan monooleate, POE-sorbitan monostearate, and POE-sorbitan tetraoleate); POE sorbitol fatty acid esters (such as POE-sorbitol monolaurate, POE-sorbitol monooleate, POE-sorbitol pentaoleate, and POE-sorbitol monostearate); POE-glycerol fatty acid esters (such as POE-monooleates, POE-glycerol monostearate, POE-glycerol monoisostearate, and POE-glycerol triisostearate); POE-fatty acid esters (such as POE-distearate, POE-monodioleate, and ethylene glycol distearate); POE-alkyl ethers (such as POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, and POE-cholestanol ether); Pluronic type surfactants (such as Pluronic); POE/POP-alkyl ethers (such as POE/POP cetyl ether, POE/POP 2-decyltetradecyl ether, POE/POP monobutyl ether, POE/POP hydrogenated lanolin, and POE/POP glycerol ether); tetra POE/tetra POP-ethylenediamine condensates (such as Tetronic); POE-castor oil or hardened castor oil derivatives (such as POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamate monoisostearate diester, and POE-hardened castor oil maleate); POE-beeswax lanolin derivatives (such as POE-sorbitol beeswax); alkanolamides (such as coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, and fatty acid isopropanolamide); POE-propylene glycol fatty acid esters; POE-alkylamines; POE-fatty acid amides; sucrose fatty acid esters; alkylethoxydimethylamine oxides; and trioleyl phosphate.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives such as, for example, the quaternized hydroxyethyl cellulose obtainable from Amerchol under the name of Polymer JR 400, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone/vinyl imidazole polymers such as, for example, Luviquat (BASF), condensation products of polyglycols and amines, quaternized collagen polypeptides such as, for example, Lauryidimonium Hydroxypropyl Hydrolyzed Collagen, quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers such as, for example, Amodimethicone, copolymers of adipic acid and dimethylamino-hydroxypropyl diethylenetriamine (Cartaretine, Sandoz), copolymers of acrylic acid with dimethyl diallyl ammonium chloride, polyquaternium type polymers, polyaminopolyamides and crosslinked water-soluble polymers thereof, cationic chitin derivatives such as, for example, quaternized chitosan, optionally in micro-crystalline distribution, condensation products of dihaloalkyls, for example dibromobutane, with bis-dialkylamines, for example bis-dimethylamino-1,3-propane, cationic guar gum such as, for example, Jaguar CBS, Jaguar C-17, Jaguar C-16 of Celanese, quaternized ammonium salt polymers such as, for example, Mirapol A-15, Mirapol AD-1, Mirapol AZ-1 of Mirapol.
  • Suitable anionic, zwitterionic, amphoteric and nonionic polymers are, for example, vinyl acetate/crotonic acid copolymers, vinyl pyrrolidone/vinyl acrylate copolymers, vinyl acetate/butyl maleate/isobornyl acrylate copolymers, methyl vinylether/maleic anhydride copolymers and esters thereof, uncrosslinked and polyol-crosslinked polyacrylic acids, acrylamidopropyl trimethylammonium chloride/acrylate copolymers, octylacrylamide/methyl methacrylate/tert.-butylaminoethyl methacrylate/2-hydroxypropyl methacrylate copolymers, polyvinyl pyrrolidone, vinyl pyrrolidone/vinyl, acetate copolymers, vinyl pyrrolidone/dimethylaminoethyl methacrylate/vinyl caprolactam terpolymers and optionally derivatized cellulose ethers and silicones.
  • Examples of UV protection factors include organic substances (light filters) which are liquid or crystalline at room temperature and which are capable of absorbing ultraviolet radiation and of releasing the energy absorbed in the form of longer-wave radiation, for example heat. UV-B filters can be oil-soluble or water-soluble. The following are examples of oil-soluble substances: 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3-(4-methylbenzylidene)-camphor; 4-aminobenzoic acid derivatives, preferably 4-(dimethylamino)-benzoic acid-2-ethylhexyl ester, 4-(dimethylamino)-benzoic acid-2-octyl ester and 4-(dimethylamino)-benzoic acid
  • Amylester; esters of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid-2-ethylhexyl ester (Octocrylene); esters of salicylic acid, preferably salicylic acid-2-ethylhexyl ester, salicylic acid-4-isopropylbenzyl ester, salicylic acid homomethyl ester;derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzo-phenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic acid di-2-ethylhexyl ester; triazine derivatives such as, for example, 2,4,6-trianilino-(p-carbo-2'-ethyl-1'-hexyloxy)-1,3,5-triazine and Octyl Triazone; propane-1,3-diones such as, for example, 1-(4-tert.butylphenyl)-3-(4T-methoxyphenyl)-propane-1,3-dione; 2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts thereof; sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and salts thereof; sulfonic acid derivatives of 3-benzylidene camphor such as, for example, 4-(2-oxo-3-bornylidenemethyl)-benzene sulfonic acid and 2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and salts thereof.
  • Typical UV-A filters are, in particular, derivatives of benzoyl methane such as, for example 1-(4'-tert.butylphenyl)-3-(4'-methoxyphenyl)-propane-1,3-dione, 4-tert-butyl-4'-methoxydibenzoyl methane (Parsol 1789) or 1-phenyl-3-(4'-isopropylphenyl)-propane-1,3-dione.
  • The UV-A and UV-B filters may of course also be used in the form of mixtures. Besides the soluble substances mentioned, insoluble pigments, i.e. finely dispersed metal oxides or salts, may also be used for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and also oxides of iron, zirconium, silicon, manganese, aluminium and cerium and mixtures thereof. Silicates (talcum), barium sulfate and zinc stearate may be used as salts. The oxides and salts are used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and more preferably from 15 to 30 nm. They may be spherical in shape although ellipsoidal particles or other non-spherical particles may also be used. The pigments may also be surface-treated, i.e. hydrophilicized or hydrophobicized. Typical examples are coated titanium dioxides such as, for example, Titandioxid T 805 (Degussa) or Eusolex T2000 (Merck). Suitable hydrophobic coating materials are, above all, silicones and especially trialkoxyoctyl silanes or simethicones. So-called micro- or nanopigments are preferably used in sun protection products. Micronized zinc oxide is preferably used.
  • Besides the two above-mentioned groups of primary protection factors, secondary protection factors of the antioxidant type may also be used. Secondary sun protection factors of the antioxidant type interrupt the photochemical reaction chain which is initiated when UV rays penetrate into the skin. Typical examples of suitable antioxidants are amino acids (for example glycine, histidine, tyrosine, tryptophane) and derivatives thereof, imidazoles (for example urocanic acid) and derivatives thereof, peptides, such as D,L-carnosine, D-carnosine, L-carnosine and derivatives thereof (for example anserine), carotinoids, carotenes (for example α-carotene, β-carotene, lycopene) and derivatives thereof, chlorogenic acid and derivatives thereof, liponic acid and derivatives thereof (for example dihydroliponic acid), aurothioglucose, propylthiouracil and other thiols (for example thioredoxine, glutathione, cysteine, cystine, cystamine and glycosyl, N-acetyl, methyl, ethyl, propyl, amyl, butyl and lauryl, palmitoyl, oleyl, γ-linoleyl, cholesteryl and glyceryl esters thereof) and their salts, dilaurylthiodipropionate, distearylthiodipropionate, thiodipropionic acid and derivatives thereof (esters, ethers, peptides, lipids, nucleotides, nucleosides and salts) and sulfoximine compounds (for example butionine sulfoximines, homocysteine sulfoximine, butionine sulfones, penta-, hexa- and hepta-thionine sulfoximine) in very small compatible dosages (also (metal) chelators (for example (α-hydroxyfatty acids, palmitic acid, phytic acid, lactoferrine), α-hydroxy acids (for example citric acid, lactic acid, malic acid), humic acid, bile acid, bile extracts, bilirubin, biliverdin, EDTA, EGTA and derivatives thereof, unsaturated fatty acids and derivatives thereof (for example γ-linolenic acid, linoleic acid, oleic acid), folic acid and derivatives thereof, ubiquinone and ubiquinol and derivatives thereof, vitamin C and derivatives thereof (for example ascorbyl palmitate, Mg ascorbyl phosphate, ascorbyl acetate), tocopherols and derivatives (for example vitamin E acetate), vitamin A and derivatives (vitamin A palmitate) and coniferyl benzoate of benzoin resin, rutinic acid and derivatives thereof, (α-glycosyl rutin, ferulic acid, furfurylidene glucitol, carnosine, butyl hydroxytoluene, butyl hydroxyanisole, nordihydroguaiac resin acid, nordihydroguaiaretic acid, trihydroxy-butyrophenone, uric acid and derivatives thereof, mannose and derivatives thereof, Superoxid-Dismutase, zinc and derivatives thereof (for example ZnO, ZnSO4), selenium and derivatives thereof (for example selenium methionine), stilbenes and derivatives thereof (for example stilbene oxide, trans-stilbene oxide) and derivatives of these active substances suitable for the purposes of the invention (salts, esters, ethers, sugars, nucleotides, nucleosides, peptides and lipids).
  • Examples of metal ion sequestering agents include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid 4Na salt, disodium edetate, trisodium edetate, tetrasorium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, and trisodium hydroxyethyl ethylenediamine triacetate.
  • Examples of vitamins include vitamins A, B1, B2, B6, C, and E and the derivatives thereof; pantothenic acid and the derivatives thereof; and biotin.
  • Examples of antioxidants include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, and gallic acid esters. Examples of antioxidant aids include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, lactic acid, fumaric acid, cephalin, hexametaphosphates, phytic acid, and ethylenediaminetetraacetic acid.
  • Suitable perfume oils are mixtures of natural and synthetic fragrances. Natural fragrances include the extracts of blossoms (lily, lavender, rose, jasmine, neroli, ylang-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel (bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamon, costus, iris, calmus), woods (pinewood, sandalwood, guaiac wood, cedarwood, rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme), needles and branches (spruce, fir, pine, dwarf pine), resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials, for example civet and beaver, may also be used. Typical synthetic perfume compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Examples of perfume compounds of the ester type are benzyl acetate, phenoxyethyl isobutyrate, p-tert-butyl cyclohexylacetate, linalyl acetate, dimethyl benzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethylmethyl phenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether while aldehydes include, for example, the linear alkanals containing 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, filial and bourgeonal. Examples of suitable ketones are the ionones, α-isomethylionone and methyl cedryl ketone. Suitable alcohols are anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include the terpenes and balsams. However, it is preferred to use mixtures of different perfume compounds which, together, produce an agreeable fragrance. Other suitable perfume oils are essential oils of relatively low volatility which are mostly used as aroma components. Examples are sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime-blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavendin oil. The following are preferably used either individually or in the farm of mixtures: bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, α-nexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, sandelice, citrus oil, mandarin oil, orange oil, allylamyl glycolate, cyclovertal, lavendin oil, clary oil, β-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat.
  • Typical examples of germ inhibitors are preservatives which act specifically against gram-positive bacteria such as, for example, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di-(4-chlorophenyl-biguanido)-hexane) or TCC (3,4,4'-trichlorocarbanilide). Numerous perfumes and essential oils also have antimicrobial properties. Typical examples are the active substances eugenol, menthol and thymol in clove, mint and thyme oil.
  • The following examples are given in order to provide a person skilled in the art with a sufficiently clear and complete explanation of the present invention, but should not be considered as limiting of the essential aspects of its subject, as set out in the preceding portions of this description.
  • EXAMPLES Preparation of solid composition according to the invention
  • In the following a non-limiting example for the preparation of a solid composition according to the invention is provided (general method).
  • 220 grams of palm fatty acid acid were introduced in an inert atmosphere into a stainless steel reactor, and 74.9 grams of triethanolamine were added with stirring. The mixture was heated for at least 4 hours at 160-180°C in order to remove the water of the reaction. The progress of the reaction was monitored by an acid/base assay which determines the residual acidity to obtain an esterification of at least 90% of the fatty acids. 280.4g of a yellowish liquid product, consisting essentially of a mixture of unesterified fatty acids, mono-, di- and triesterified triethanolamine and unreacted triethanolamine amine may also remain. For the quaternisation, 58.1 grams of dimethyl sulphate were added with stirring at a temperature of 50-90°C to 271.4 grams of the product obtained from the esterification. After four hours of digestion, the virtually complete absence of residual amine was verified by acid/base assay. After obtain 329.5 grams of the esterquat (EQ-HC) were diluted with 989.1 grams of cetearyl alcohol. Keeping the product under inert and stirring conditions, 133.9 grams of behenamidopropyldimethylamine were added to have a complete homogenization. Once the product was homogeneous it was cooled down to room temperature. Some of the compositions were neutralized with lactic acid in order to form the amine salt of the amidoamine (cationic surfactant) and some of them were not neutralized.
  • Table 1 shows the ingredients used to prepared solid compositions. The amounts for each component indicated in Table 1 are indicated in percentage of active weight of each ingredient, and were prepared following the general method.
  • Table 2 summarizes the physical properties of the compositions prepared in defined in Table 1. Table 1
    % A B C D E F G H C1
    EQ HC1 22,7 22,1 22,7 22,1 14, 6 14,2 14,7 14,2 -
    Cetyl Alcohol - - - - 36,7 35,7 36,8 35,7 -
    Stearyl Alcohol - - - - 36,7 35,7 36,8 35,7 -
    Cetearyl Alcohol (50:50) 68,0 66,5 68,2 66,5 - - - - 66,6
    Behenamido propyldime thylamine 9,21 9,00 - - 11,8 11,5 - - -
    Stereamido propyldime thylamine - - 8,98 8,75 - - 11,6 11,2 13,4
    Lactic Acid 90% - 2,31 - 2,57 - 2,71 - 3,03 3,22
    Behentrimo nium Chloride - - - - - - - - 16,7
    Ratio (a) : (b) 2,46 :1 1, 96 :1 2,53 :1 1,96 :1 1,23 :1 1:1 1,27 :1 1:1 1,25 :1 (* )
    (*) In this case the ratio a:b does not apply, the figure 1,25:1 refers to the weight ratio between the quaternary ammonium compound and the amidoamine.
    Table 2
    A B C D E F G H
    Hygroscopicity (20°C, 80%HR, 48h) O Δ O Δ O Δ Δ
    Penetrability (1/10mm, 150g, 30sec) Δ Δ
    Rheology
    ⊙, ○, Δ, X : Excellent, good, fair,bad
  • All products in Table 2 are light colored solids, and their melting point (Differential Scanning Calorimeter DSC-Q20 (TA Instruments)) is between 60 and 70°C.
  • Hygroscopicity was measured by storing the sample at 20°C and 80% relative humidity and weighting the sample after specific times under these conditions.
  • Hardness was indirectly measured by penetrability by using a penetrometer (Normatest). The higher the penetrability the lower the hardness of the sample is.
  • Samples with penetrability below 30 and melting points above 43°C are considered able to make pellets.
  • Samples were melted and let cool down to room temperature for 24 hours before measuring penetrability. The applied weight for the measurements was 150g during 30 seconds and the penetrability of the needle was read in the penetrometer.
  • Rheograms of viscosity vs. temperature were measured by using a Haake Rhestress 600 rheometer (Thermo-Fischer) in order to find out the fluidity of each composition. Conditions: 85 to 30°C, ω=201/s, #13.
  • For all the properties, the compositions comprising Behenamidopropyl Dimethylamine, i.e. samples A, B, E and F, are preferred. Not neutralized samples (A and E) are even more preferred.
  • Dispersing ability at room temperature
  • All the samples described Table 1 are light colored solids, but only samples A, B, E and F of Table 1, containing the esterquat, Behenamidopropyl Dimethylamine and fatty alcohol are able to disperse at room temperature in water only by mechanical stirring, and without the need of heating.
  • The dispersing ability in water at room temperature was evaluated after preparing 300 grams of sample by stirring the compositions described above (1,5% active cationic (esterquat and amidoamine) and 3% fatty alcohol) in water for 2 hours at 25°C at 250 rpm. Then samples were filtered by an ASTM 50 filter (300 micron) under pressure. The residue left on the filter was then dried for 24 hours at 50°C and weighted. Only compositions A, B, E and F were possible to filter completely. Thus, these composition are preferred having regard to the present invention.
  • In the rest of the samples, a big solid residue made impossible to complete the filtration of the sample. This indicates that these products could not be completely dispersed at room temperature.
  • Performance in hair conditioner composition
  • Performance was also evaluated in formulations shown in Table 3. Combing force of hair conditioners prepared containing esterquat and amidoamines at two different ratios (all ratios are in active matter). All formulations contain 1,5% active cationic (quaternary ester ammonium compound and amidoamine) and 3% fatty alcohol.
  • Combing force reduction is one of the advantageous characteristics of the composition, as it is a measure of a good performance.
  • Combing forces were determined using a dynamometer (Instron 5543, cell 1 kg, rate 500 mm/min). A Caucasian damaged hair tress of approximately 20 g and 22 cm in length was combed 10 times under wet and dry conditions and the values obtained were averaged.
  • As can be seen, the compositions according to the invention have very low combing forces. Table 3
    Weight Ratio Combing force (gf)
    EQ HC+
    Behenamidopropyldimethylamine 2:1 77
    EQ HC+
    Behenamidopropyldimethylamine 1:1 92
    Behenamidopropyldimethylamine 86
    EQ HC 111

Claims (19)

1. A composition comprising:
- one or more quaternary ester ammonium compounds (a),
- one or more amidoamine compounds (b),
- one or more fatty alcohols (c),
wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:5 to 5:1.
2. The composition according to claim 1, wherein the one or more quaternary ester ammonium compounds (a) comprise at least a compound represented by formula (I)
Figure imgb0006
wherein
X1 represents an hydroxyalkyl group containing 1 to 4 carbon atoms or an alkyl group containing 1 to 4 carbon atoms or an alkyl group containing one aromatic group, preferably X1 is an alkyl group containing 1 to 4 carbon atoms, more preferably X1 is a methyl group;
R1 is a linear or branched alkyl or alkenyl group containing from 5 to 23 carbon atoms and from 0 to 3 double bonds,
R2 and R3 each independently represent H, OH or -O-Lq-C(O)-R1,
L represents a -(OCH2CH2)a-(OR4CHCH2)b- group, wherein R4 represents an alkyl group containing 1-4 carbon atoms, a represents an average number within the range of 0 to 20, b represents an average number within the range of 0 to 6, and the sum of a+b represents an average number within the range of 0 to 26,
q represents an average number within the range from 0 to 26, m, n, and p each independently represent an average number within the range of 1 to 4, and
A represents an anion, preferably an halide, phosphate or alkylsulphate.
3. The composition according to claim 1 or 2, wherein the one or more amidoamine compounds (b) comprise at least a compound represented by formula (II)
Figure imgb0007
wherein
R1 represents a linear or branched, saturated or unsaturated alkyl chain group containing from 8 to 36 carbon atoms,
R2 represents a linear or branched alkylene group containing from 1 to 6 carbon atoms, and
R3 and R4 each independently represent a linear or branched alkyl group containing 1 to 3 carbon atoms.
4. The cosmetic composition according to any one of claims 1 to 3, wherein the fatty alcohols (c) comprise fatty alcohols containing from 6 to 22 carbon atoms, preferably the fatty alcohols (c) are fatty alcohols containing from 6 to 22 carbon atoms derived from natural fat and/or natural oil.
5. The composition according to any one of claims 1 to 4, wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is within a range of 1:3 to 3:1.
6. The composition according to any one of claims 1 to 5 further comprising an organic and/or inorganic acid.
7. The composition according to any one of claims 1 to 6, wherein the one or more amidoamine compounds (b) is behenamidopropyl dimethylamine.
8. The composition according to any one of claims 1 to 7, wherein the weight ratio between the one or more quaternary ester ammonium compounds (a) and the one or more amidoamine compounds (b) is 2:1.
9. The composition according to any one of claims 1 to 8, wherein water content is 10 wt.-% or less and the composition is characterized in that the composition is solid at room temperature.
10. The composition according to claim 9, wherein the composition is free of an organic and/or inorganic acid.
11. The composition according to claims 9 or 10, wherein the water content of the composition is 0.2 wt.-% or less.
12. The composition according to claims 9 to 11, comprising:
- 2.5% to 42%, preferably 13% to 25%, more preferably 20% to 24%, of the one or more quaternary ester ammonium compounds (a),
- 2.5% to 42%, preferably 6% to 25%, more preferably 7% to 15%, of the one or more amidoamine compounds (b),
- 50% to 83%, preferably 60% to 75%, more preferably 65% to 70%,
of the one or more fatty alcohols (c),
wherein the amounts indicated are expressed as percentage by active weight (with respect to the total weight of the composition).
13. The composition according to claim 1 to 8 for use as a hair conditioner.
14. The composition according to claim 13, wherein the water content of the composition is more than 10 wt.-%.
15. A method to obtain a composition for use as defined in claims 13, comprising a step a) of dispersing the composition as defined in any one of claims 9-12 in water, wherein the method is carried out at a temperature within a range of 15°C to 40°C, preferably within a range of 18 to 35°C, more preferably within a range of 20 to 30°C, most preferably at room temperature.
16. The method according to claim 15, wherein the water content of the composition as defined in claim 15 is more than 10 wt.-%.
17. The method according to claims 15 or 16, further comprising a step b) carried out after step a), wherein step b) further comprises the addition of an organic and/or inorganic acid.
17. Use of a composition according to any one of claims 1 to 14 or obtained according to the method as defined in any one of claims 15 to 17 for the conditioning treatment of hair.
18. Method of conditioning human hair, characterized in that the composition according to any one of claims 1 to 14 or the composition obtained in the method as defined in any one of claims 15 to 17 is applied to hair.
EP20130382248 2013-06-26 2013-06-26 Hair conditioner Withdrawn EP2818155A1 (en)

Priority Applications (13)

Application Number Priority Date Filing Date Title
EP20130382248 EP2818155A1 (en) 2013-06-26 2013-06-26 Hair conditioner
PCT/EP2014/063119 WO2014206920A1 (en) 2013-06-26 2014-06-23 Hair conditioner
MX2015016500A MX353750B (en) 2013-06-26 2014-06-23 Hair conditioner.
PT147340749T PT3013312T (en) 2013-06-26 2014-06-23 Hair conditioner
BR112015032424-0A BR112015032424B1 (en) 2013-06-26 2014-06-23 composition for hair conditioner, its method of preparation, use and method of hair conditioning
DK14734074.9T DK3013312T3 (en) 2013-06-26 2014-06-23 HAIR CONDITIONER
EP14734074.9A EP3013312B1 (en) 2013-06-26 2014-06-23 Hair conditioner
JP2016522425A JP6194420B2 (en) 2013-06-26 2014-06-23 Hair conditioner
RU2016102165A RU2676695C2 (en) 2013-06-26 2014-06-23 Hair conditioner
CA2914141A CA2914141C (en) 2013-06-26 2014-06-23 Hair conditioner compositions comprising behenamidopropyl dimethylamine, a quaternary ester ammonium compound, and a fatty alcohol
US14/901,369 US10617619B2 (en) 2013-06-26 2014-06-23 Hair conditioner
ES14734074.9T ES2648598T3 (en) 2013-06-26 2014-06-23 Hair conditioner
PL14734074T PL3013312T3 (en) 2013-06-26 2014-06-23 Hair conditioner

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20130382248 EP2818155A1 (en) 2013-06-26 2013-06-26 Hair conditioner

Publications (1)

Publication Number Publication Date
EP2818155A1 true EP2818155A1 (en) 2014-12-31

Family

ID=48703384

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20130382248 Withdrawn EP2818155A1 (en) 2013-06-26 2013-06-26 Hair conditioner
EP14734074.9A Active EP3013312B1 (en) 2013-06-26 2014-06-23 Hair conditioner

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP14734074.9A Active EP3013312B1 (en) 2013-06-26 2014-06-23 Hair conditioner

Country Status (12)

Country Link
US (1) US10617619B2 (en)
EP (2) EP2818155A1 (en)
JP (1) JP6194420B2 (en)
BR (1) BR112015032424B1 (en)
CA (1) CA2914141C (en)
DK (1) DK3013312T3 (en)
ES (1) ES2648598T3 (en)
MX (1) MX353750B (en)
PL (1) PL3013312T3 (en)
PT (1) PT3013312T (en)
RU (1) RU2676695C2 (en)
WO (1) WO2014206920A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020076881A1 (en) * 2018-10-10 2020-04-16 The Procter & Gamble Company Personal care product customized by discrete particles and method of apply thereof
WO2021239335A1 (en) * 2020-05-26 2021-12-02 Rhodia Operations Method for preparing a fatty amidoalkyldialkylamine
EP4014952A1 (en) * 2020-12-17 2022-06-22 Kao Corporation Solid composition for keratin fibers

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX2012015187A (en) 2010-07-02 2013-05-09 Procter & Gamble Method for delivering an active agent.
CA2803636C (en) 2010-07-02 2017-05-16 The Procter & Gamble Company Detergent product and method for making same
BR112013000101A2 (en) 2010-07-02 2016-05-17 Procter & Gamble filaments comprising active agent nonwoven webs and methods of manufacture thereof
WO2015164227A2 (en) 2014-04-22 2015-10-29 The Procter & Gamble Company Compositions in the form of dissolvable solid structures
EP4245296B1 (en) 2017-01-27 2024-07-17 The Procter & Gamble Company Compositions in the form of dissolvable solid structures
CN110167639B (en) 2017-01-27 2022-10-14 宝洁公司 Composition in the form of a soluble solid structure comprising effervescent agglomerated granules
EP3609467B1 (en) 2017-04-13 2024-02-28 The Procter & Gamble Company Method of preparing a product composition comprising a discrete particle and an aqueous base composition
EP3624765A1 (en) 2017-05-16 2020-03-25 The Procter and Gamble Company Conditioning hair care compositions in the form of dissolvable solid structures
FR3080038B1 (en) * 2018-04-16 2020-10-09 Oreal COSMETIC COMPOSITION FOR KERATINIC FIBERS
CN112261931B (en) 2018-06-05 2023-12-08 宝洁公司 Transparent cleaning composition
EP3597172A1 (en) * 2018-07-16 2020-01-22 Kao Germany GmbH Hair treatment composition
JP1639110S (en) 2018-07-16 2019-08-13
US11666514B2 (en) 2018-09-21 2023-06-06 The Procter & Gamble Company Fibrous structures containing polymer matrix particles with perfume ingredients
JP7328336B2 (en) 2018-12-14 2023-08-16 ザ プロクター アンド ギャンブル カンパニー SHAMPOO COMPOSITION CONTAINING SHEET-FORMED MICROCAPSULES
EP3989913A1 (en) 2019-06-28 2022-05-04 The Procter & Gamble Company Dissolvable solid fibrous articles containing anionic surfactants
US11896689B2 (en) 2019-06-28 2024-02-13 The Procter & Gamble Company Method of making a clear personal care comprising microcapsules
MX2021015391A (en) 2019-07-03 2022-01-24 Procter & Gamble Fibrous structures containing cationic surfactants and soluble acids.
USD939359S1 (en) 2019-10-01 2021-12-28 The Procter And Gamble Plaza Packaging for a single dose personal care product
MX2022002875A (en) 2019-10-14 2022-03-25 Procter & Gamble Biodegradable and/or home compostable sachet containing a solid article.
CN114727933B (en) 2019-11-20 2024-03-08 宝洁公司 Porous dissolvable solid structure
WO2021113211A1 (en) 2019-12-01 2021-06-10 The Procter & Gamble Company Hair conditioner compositions with a preservation system containing sodium benzoate and glycols and/or glyceryl esters
JP7453395B2 (en) 2020-02-14 2024-03-19 ザ プロクター アンド ギャンブル カンパニー A bottle adapted for the storage of a liquid composition having an aesthetic design suspended therein
USD941051S1 (en) 2020-03-20 2022-01-18 The Procter And Gamble Company Shower hanger
USD962050S1 (en) 2020-03-20 2022-08-30 The Procter And Gamble Company Primary package for a solid, single dose beauty care composition
USD965440S1 (en) 2020-06-29 2022-10-04 The Procter And Gamble Company Package
JP7506249B2 (en) 2020-07-31 2024-06-25 ザ プロクター アンド ギャンブル カンパニー Hair care prill-containing water-soluble fiber pouch
CN116456957A (en) 2020-08-11 2023-07-18 宝洁公司 Low viscosity hair conditioner compositions containing valine ester ethane sulfonate of brassinolide
WO2022036353A1 (en) 2020-08-11 2022-02-17 The Procter & Gamble Company Moisturizing hair conditioner compositions containing brassicyl valinate esylate
JP2023535385A (en) 2020-08-11 2023-08-17 ザ プロクター アンド ギャンブル カンパニー Clean rinse hair conditioner composition containing brassy silver valinate esylate
CA3201309A1 (en) 2020-12-01 2022-06-09 The Procter & Gamble Company Aqueous hair conditioner compositions containing solubilized anti-dandruff actives
USD1045064S1 (en) 2020-12-17 2024-10-01 The Procter & Gamble Company Single-dose dissolvable personal care unit
US11633072B2 (en) 2021-02-12 2023-04-25 The Procter & Gamble Company Multi-phase shampoo composition with an aesthetic design
US12053130B2 (en) 2021-02-12 2024-08-06 The Procter & Gamble Company Container containing a shampoo composition with an aesthetic design formed by bubbles

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988003016A1 (en) * 1986-10-23 1988-05-05 Stevens Frank H Particulate emulsifiable hair conditioning composition
ES2021900A6 (en) 1989-07-17 1991-11-16 Pulcra Sa Process for preparing quaternary ammonium compounds.
EP0786250A1 (en) 1996-01-23 1997-07-30 Henkel Kommanditgesellschaft auf Aktien Composition for reviving hair
WO1997031617A1 (en) * 1996-02-28 1997-09-04 The Procter & Gamble Company Mild hair conditioning compositions
EP1254653A1 (en) * 2001-04-30 2002-11-06 Cognis Iberia, S.L. Use of cationic compositions
EP2138156A1 (en) * 2008-06-27 2009-12-30 Beiersdorf AG Hair conditioner preparation with a special mixture of cationic conditioners
EP2335678A1 (en) * 2009-12-18 2011-06-22 KPSS-Kao Professional Salon Services GmbH Conditioning composition for hair
EP2394632A1 (en) 2009-02-03 2011-12-14 Shiseido Co., Ltd. Hair conditioner composition and low-energy manufacturing method for the same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6274128B1 (en) * 1998-12-23 2001-08-14 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Self-warming hair conditioning compositions
BRPI0211039B1 (en) * 2001-06-22 2015-07-14 Unilever Nv Solid hair conditioner and use of a solid hair conditioner
GB2383950B (en) * 2002-01-11 2006-01-18 Cosmetic Warriors Ltd Cosmetic product
WO2004093834A1 (en) * 2003-04-17 2004-11-04 Croda, Inc. Personal care product containing diester quat
US20070292380A1 (en) * 2006-06-16 2007-12-20 James Anthony Staudigel Hair conditioning composition containing a non-guar galactomannan polymer derivative
EP2316414B1 (en) * 2008-08-08 2016-03-30 Shiseido Company, Ltd. Hair conditioner composition
EP2426101A1 (en) * 2010-08-05 2012-03-07 Cognis IP Management GmbH Cosmetic preparations
BR112013002243A2 (en) * 2010-08-10 2016-05-24 Croda Inc "Personal Care Product, Diester, Lozenge Composition, and Compound."

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988003016A1 (en) * 1986-10-23 1988-05-05 Stevens Frank H Particulate emulsifiable hair conditioning composition
ES2021900A6 (en) 1989-07-17 1991-11-16 Pulcra Sa Process for preparing quaternary ammonium compounds.
EP0786250A1 (en) 1996-01-23 1997-07-30 Henkel Kommanditgesellschaft auf Aktien Composition for reviving hair
WO1997031617A1 (en) * 1996-02-28 1997-09-04 The Procter & Gamble Company Mild hair conditioning compositions
EP1254653A1 (en) * 2001-04-30 2002-11-06 Cognis Iberia, S.L. Use of cationic compositions
US20040146478A1 (en) 2001-04-30 2004-07-29 Queralt Esther Prat Use of cationic preparations
EP2138156A1 (en) * 2008-06-27 2009-12-30 Beiersdorf AG Hair conditioner preparation with a special mixture of cationic conditioners
EP2394632A1 (en) 2009-02-03 2011-12-14 Shiseido Co., Ltd. Hair conditioner composition and low-energy manufacturing method for the same
EP2335678A1 (en) * 2009-12-18 2011-06-22 KPSS-Kao Professional Salon Services GmbH Conditioning composition for hair

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
M. MINGUET ET AL: "Behenamidopropyl Dimethylamine: unique behaviour in solution and in hair care formulations", INTERNATIONAL JOURNAL OF COSMETIC SCIENCE, vol. 32, no. 4, 1 August 2010 (2010-08-01), pages 246 - 257, XP055073838, ISSN: 0142-5463, DOI: 10.1111/j.1468-2494.2009.00566.x *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020076881A1 (en) * 2018-10-10 2020-04-16 The Procter & Gamble Company Personal care product customized by discrete particles and method of apply thereof
CN112804984A (en) * 2018-10-10 2021-05-14 宝洁公司 Personal care products customized from discrete particles and methods of applying same
CN112804984B (en) * 2018-10-10 2024-05-28 宝洁公司 Personal care products tailored from discrete particles and methods of application thereof
WO2021239335A1 (en) * 2020-05-26 2021-12-02 Rhodia Operations Method for preparing a fatty amidoalkyldialkylamine
EP4014952A1 (en) * 2020-12-17 2022-06-22 Kao Corporation Solid composition for keratin fibers

Also Published As

Publication number Publication date
EP3013312A1 (en) 2016-05-04
EP3013312B1 (en) 2017-08-30
US20160143827A1 (en) 2016-05-26
ES2648598T3 (en) 2018-01-04
PL3013312T3 (en) 2017-12-29
RU2016102165A (en) 2017-07-27
RU2676695C2 (en) 2019-01-10
CA2914141A1 (en) 2014-12-31
JP2016523872A (en) 2016-08-12
US10617619B2 (en) 2020-04-14
DK3013312T3 (en) 2017-10-09
MX2015016500A (en) 2016-09-28
BR112015032424B1 (en) 2020-12-01
BR112015032424A2 (en) 2017-08-22
JP6194420B2 (en) 2017-09-06
MX353750B (en) 2018-01-26
WO2014206920A1 (en) 2014-12-31
CA2914141C (en) 2020-12-29
PT3013312T (en) 2017-10-04

Similar Documents

Publication Publication Date Title
EP3013312B1 (en) Hair conditioner
EP1739161B1 (en) Foam-enhancing agent
US6740130B2 (en) Hair-colorant preparations and methods of using the same
US11826450B2 (en) Cosmetic compositions
EP1661976A1 (en) Ethercarboxylates and glycerine derivatives as foam-enhancing agent for surfactants
US8246697B2 (en) Mixture of amides and cosmetic compositions comprising said mixture
WO2018221606A1 (en) Cosmetic
US6569410B1 (en) Sun protection compositions containing UV protection factors and esters of hydroxycarboxylic acids and alk(en)yl oligoglycosides
EP1661547A1 (en) Foam-enhancing agent containing polyglycerol
EP4019616A1 (en) Quaternary ester ammonium compound compositions
EP1672054A1 (en) Carboxymethylated glyceride derivatives as foam-enhancing agents for surfactants
JP2004532255A (en) Hair care formulations containing natural oils
EP4438031A1 (en) A process for preparing a composition comprising a carboxyalkylated alkyl- and/or alkenylglycoside, and the composition obtainable by this process
EP4260843A1 (en) Composition comprising an alkyl and/or alkenylglycoside derivative and an ester derived from a hydroxycarboxylic acid and a fatty alcohol
US7001591B1 (en) Cosmetic preparations containing silicone compounds and esters of hydroxycarboxylic acids and alk(en)yl oligoglycosides
EP4438032A1 (en) Composition comprising an alkyl- and/or alkenylglycoside
CN116033942A (en) Oil-in-water emulsion composition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130626

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

R17P Request for examination filed (corrected)

Effective date: 20150428

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20150701